JPH02212579A - Benzene.bis-1,3-siketone derivative as ultraviolet absorbing composition - Google Patents

Abstract

PURPOSE: To prevent a substrate (e.g. plastic) from being deteriorated by locally applying a composition comprising a carrier mixed with an effective amount of an ultraviolet absorbing compound comprising a specified bis-diketone derivative.

CONSTITUTION: A substrate is protected from an influence of ultraviolet rays by locally applying thereto a composition comprising a carrier mixed with an effective amount of an ultraviolet-absorbing compound represented by formula I [wherein R and R¹ are each a 1-10C alkyl or a group represented by formula II (wherein R² and R³ are each H or a 1-4C alkyl; and Ar is phenyl or an alkyl-substituted alkyl); and A is a divalent 1,3- or 1,4-benzene radical having a group represented by formula III or IV (wherein R⁴, R⁵, R⁶ and R⁷ are each H, a 1-16C alkyl or a 1-10C alkoxyl, provided only one of them is an alkoxyl). This composition is useful to protect a substrate (e.g. plastic) from being rapidly deteriorated and to protect the skin of a warm-blooded animal from severe erythema, edema or bulla occurring upon exposure to sunlight.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides ultraviolet absorbing compositions comprising certain conjugated bis-1,3-diketone derivatives of benzene and mixtures thereof useful as protective coatings and for protecting substrates from the deleterious effects of actinic radiation. Concerning how to. Furthermore, the present invention relates to a method for producing a coating composition that absorbs ultraviolet light.

UV-absorbing coatings are useful in preventing rapid deterioration of substrates such as plastics, and in protecting the skin of warm-blooded animals from the severe erythema, edema, and blisters that occur when exposed to sunlight. The sujiketone compositions of the present invention are commonly referred to as sunscreen compositions and can be mixed with sun oils, lotions, lipsticks, hair treatments, and skin formulations.
It can also be mixed with contact lenses.

The present invention is based on the general formula r RCOCH, CO-^-COCHzCOR'
(1) [wherein -R and R1 are both straight and branched alkyl groups having 1 to 10 carbon atoms or of formula C
R2R'^r (wherein R2 and R1 are H and 1-4
selected from alkyl groups having A r
is phenyl or an alkyl-substituted phenyl group). -A- group has the formula ■
or a divalent 1,3 or 1,4 benzene radical having the formula ■. Substituent R4, Rs, R@, Rt is H
or an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, but only one of those groups attached to the aromatic ring is alkoxy It is the basis. A preferred compound is R1
and R is either tert-butyl or isopropyl, R4, RI, R@, R? is a halogen.

The method of substrate protection consists of topical application of a compound of formula I in an acceptable carrier. Of particular importance are UV in the wavelength range 290-320zz and 320-400 mm.
It is a compound that selectively absorbs radiation. The compound may be dissolved in the coating composition or may be present as a finely divided solid or as a solid dispersed in an acceptable carrier. The carrier used in the coating composition must be chosen such that it does not prevent absorption in the 290-400xm range; in some cases, interaction of the carrier with the bis-diketone can shift the absorption outside the desired range and interfere with the tolerance. Not Shiuruchino.

The compositions of the present invention contain a UVF photochromic gold compound of Formula 1 in an amount necessary to provide the desired protection against the harmful effects of ultraviolet radiation, and the concentration of the compound in one composition is such that when the composition is applied topically adjusted to provide the desired protection. The amount necessary to provide the desired protection may vary depending on the nature of the compound, ie, its extinction coefficient or substance, the type of carrier, the ultraviolet light source and its intensity, and other well-known variables.

Appropriate amounts can be easily determined by standard test methods. Suitably, an amount ranging from about 0.1% to about 50% by weight of the total weight of the UVF photochromic gold compound-ting composition, generally 1
．． Mixed in amounts from 0 to 30% by weight, with amounts ranging from 1.5 to 15% by weight being preferred.

Acceptable carriers include UV carriers to permit uniform topical application.
The term "pharmaceutically acceptable" includes any vehicle or medium with which the P Photokagold compound can be combined, and the term "pharmaceutically acceptable" means that the carrier is dermatologically non-toxic to bleeding animals and cosmetically acceptable. This is a limited term that includes jjh. However, not all carriers are useful on the skin; carriers consist of waxes, oils or creamy substances in which the drug is either in a clear solution or in a homogeneous dispersion, e.g. Can be retained as particles. Preferably,
The carrier comprises a suitable solvent or solvent mixture capable of dissolving the UVF photochromic gold compound in an effective concentration as an r-light agent when incorporated into a sunscreen formulation. Useful solvents include alcohols, ketones, esters, polyol esters, oils, hydrocarbons, chlorinated hydrocarbons, ethers, polyethers, polyether polyols and dimethyl sulfoxide, dimethylformamide, dimethylisosorbite, and isopropyl myristate. Other specialty solvents such as Such solvents are suitable for the active UV
It is believed that F photochemical gold compounds are effective only if they do not react with each other permanently and shift the total effective absorption outside the 290-400zx range. Some of the above ingredients may not be pharmaceutically acceptable but are useful for other uses.

The present invention relates to a method for protecting a substrate from the effects of ultraviolet radiation, which consists of topical application of the above compounds in a carrier.

Sunscreen compositions may be used as clear liquids or lotions consisting of water-in-oil, oil-in-water or various emulsions. Either oily, aqueous or both may be used as a carrier for the sunscreen composition; the oily material and the aqueous and oily compositions will form a continuous coating of the LI V F base compound. , such coatings also provide long-term protection against solar erythema. Sunscreen formulations are commonly used in hot weather and at beaches where people enjoy swimming in the sea. It is also important that the protective coating applied to the skin is not affected by water or perspiration. The reagent-acceptable compositions disclosed herein are included in a thin protective coating on the skin of bleeding animals, provide long-term protection against erythema, and provide significant protection over practical exposure times to sunlight. is not decomposed.

Generally, the compounds are synthesized by condensing the diester of the related ketone with a diester such as dimethyl terephthalate in an inert solvent such as tetrahydrophthane or n-butyl ether.

The following compounds have the formula (r); RCOCII, CO-^-COCH2COR'
The active compounds in (1) are exemplified, but not limited to.

1.1'-(1,4-phenylene)-bis-4,4-dimethylpentane-1,3-dione 1.1'-(1,3-phenylene)-bis-4,4-dimethylpentane-1 ,3-dione 1.1'-(1,4-phenylene)-bis-4-methylpentane-1,3-dione 1.1'-(1,4-phenylene)-bis-6-methylpentane-1 ,3-dione 1.1'-(1,4-phenylene)-bis-pentane-
1,3-dione 1.1"-(1,4-phenylene)-bis-5-methylhexane-1,3-dione 1.1'-(2,3,5-)tumethyl-1,4-phenylene )-bis-4-methylpentane-1,3-dione 1
．． 1'-(2,3,5,6-titramethyl-1.4-)
Unishin)-bis-4-methylpentane-1,3-dione 1.1'-(2-ethoxy-3,5-dimethyl-1,
4-phenylene)-bis-4-methylpentane-1,3
-dione 1.1'-(3-butyl-1,4-7enylene)-bis-4,4-dimethylpentane-1,3-dione 1.1'-(1,4-phenylene)-bis-4 -Phenylbutane-1,3-dione Compounds in which R and R1 are alkyl groups can be prepared by reacting the aromatic diester with the appropriate ketone erulate in an inert solvent. Substituted aromatic diesters have been described by Wals et al.
av, Chim, Pays-Bas, 87.6
5 (1968)). R and R' are CR2R3Ar
Compounds can be prepared by reacting the relevant diacetylbenzene with the appropriate ester of phenylacetic acid or substituted phenylacetic acid.

The following production examples are provided as illustrative rather than limiting representations of the monsters included in the present invention,
All parts and percentages are expressed on a weight basis unless otherwise specified.

150a1 of dry ethyrahydrofuran was placed in a 500m/mitter flask in the presence of nitrogen. 7 for this
．． 0 with addition of 8 g (0,2 mol) of sodium amide
Pinocolon (10 g, 0.1 mol) was then added dropwise over 15 minutes, followed by stirring for a further 15 minutes. Dimethyl terephthalate (9,7y, 0.05 mol) was then added and the mixture was heated under reflux for 4 hours. The container was then cooled to room temperature and poured into cold water, the pH of which was adjusted to 5.2 with hydrochloric acid. The resulting precipitate was collected by filtration and washed with water. As a result of drying the solid, 14.29
of material (1% purity by spectrophotometric analysis) was isolated.

As a result of recrystallization from methanol, absorption peak 342zy
; Pure substance with molecular extinction coefficient -32,340 (melting point, 12
4-126°C) was obtained.

The method of Preparation Example 1 was repeated using dimethyl isophthalate in place of the muterephthalate ester of 1-11'-13-phenylene-bis-44-dimethylbentan-13-dine. This substance has a maximum absorption of 314 x m and a molecular extinction coefficient of 30,360.

This substance was produced by repeating the method of Production Example 1 using the same methyl isoamyl ketone instead of binacolon. The product had an absorption peak of 343jz and a molecular extinction coefficient of 32,313.

Following the method outlined in vJ Preparation Example 1, a chemical equivalent of methyl isoamyl ketone was used in place of binacolon. The absorption peak of the product is 344xm, and the molecular extinction coefficient is 3
It is 1,556.

EXAMPLE 1 The method of Preparation Example 1 was repeated using a chemical equivalent of methyl ethyl ketone in place of the 11'-14-phenylene-bis-pentane-13 binacolon.

The product has an absorption peak of 341mt and a molecular extinction coefficient of 28.1.
It is 22.

The reaction was stirred at ambient temperature for 30 minutes, then 2.78. 1,4-dicarboethoxy 2
．． 3.5.6-Titramethylbenzene was added over 2 minutes. The reaction was then heated to reflux for 5 hours, cooled to room temperature and poured into 300ml of ice water. The pi-t was adjusted to 2-3 with concentrated Hα and the product was isolated by filtration.

This material is prepared as 'IA' by repeating the method of Preparation Example 1 using a chemical equivalent of medyl isobutyl getone in place of binacolon. This solid has a maximum absorption peak of 3
43311 and a molecular extinction coefficient of 33.000.

Gold' (0,9hN aH (97% active) in 50m & dry T
1.72. suspended in HF. To a suspension of 1.922 ml of NaH (97% active) in 50 ml of dry THF was added 3.2 g of 1,4-diacetylbenzene/'501NT HF. The reaction was stirred at ambient temperature for 30 minutes, then 5.921 F methylphenylacetate was added over 5 minutes. The reaction was heated to reflux for 5 hours, cooled to room temperature, and heated at 300x
The pH was adjusted to 2-3 with concentrated HCl and the product was isolated by filtration.

Actinic radiation from 29011 to 320 mm provides virtually all of the burn or erythema energy, and sunburn provides most of the energy, whereas 320 to 400 mm
Actinic radiation from the arm has been proven to be a source of sunburn. The cosmetics industry has divided these spectra into the burn region tJ V -B (290-320-1) and the sunburn region U V -A (320-5400xx).

Physiologically, sun rays have an adverse effect on the human skin surface, as approximately 76% of the chance of sunburn causing sunburn is found in the LJ V-B region, and the rest is found in the UV-A region. Previously, it was desirable to eliminate most of the actinic radiation in such regions, and sunscreen lotions were formulated to be most effective in the UV-B region, but recent research has shown that UV-A Similarly, it is difficult to find a practical compound that can effectively absorb both regions, although it has been pointed out that it is desirable to absorb these regions all at once. Therefore, formulators recommend that each of the compounds be used in the UV-B1 range or [,I] to provide maximum skin protection.
There are no tun-compounds included in the definition of formula 0 that are effective over the entire range from 290 to 400+u+, which must rely on a combination of two types of compounds that are effective in either the V-A region, and therefore Two or more compounds are selected and the formulation is mixed in varying concentrations until the desired balance between burn and sunburn is achieved. Such a combination is shown in Example 13, 290-3201M
at least one compound absorbing the region and 320~
Preferably, the formulation has at least one other compound absorbing in the 400 iniJ range. At least one garbled compound is selected from the formula (■).

The use of the UV filters of the present invention is exemplified in lotion formulations that are applied topically to the surface of the skin.

The effect of the UV radiation absorber was determined by treating the 1c+y2 area of the subject's back with a predetermined amount of lotion, exposing the treated area to UV radiation for a defined period of time, and then comparing the untreated skin area with the fully covered skin. Tested on human subjects by visually comparing the areas. 5PF (Skin Protection Factor) is calculated by comparing the UV effects of protected and unprotected skin.

Besides quantifying SPF in humans, many in vitro (in viLro) and in vivo (in vivo) test methods using animal models are also widely used. Some of these methods yield results that correlate well with SPF determined in humans, and such methods are effective tools for evaluating new compounds.

The following lotions and creams are illustrative of those that may be used in the practice of this invention:
It is not limited.

In general, typical formulation techniques are well known to skilled formulators and usually require that the P-light agent be first added to the oil layer and then emulsified. For Examples 1-4, all ingredients can be mixed together and stirred with conventional equipment. In many cases, a single compound at the right concentration cannot effectively protect against the entire range of the solar U spectrum that reaches Earth, so two or more types of UV absorbers are used to provide stronger protection. Mixtures of agents are used in the mixture. To illustrate the effectiveness of the compounds of the invention in sunscreen formulations, Preparation Example 3 was formulated into creams and lotions for extensive testing. Preparation examples are shown in Table 1.

No.'' (: Takeshi) j distribution 2 Z side 1'' 1 <A,) Compound mineral oil of Production Example 3 (carnation) Stearyl alcohol cetyl alcohol silicone oil (SF-96,350es) (B) Water (deionized ) 73.95 76.85 (C) Sodium hydroxide (1 oz aqueous solution), 2 (D) [INDN 55 (Glyao), 3
5(F,) Dimethylisone rubide 0. 35 4 Components 1 and 2 are mixed and heated to 70°C. Ingredient B in a separate banquet bowl
Heat to 75°C and add to A. Add C to AB,
Then cool to 40°C. Add ingredients while stirring.

A single solution of ΔE of 3' was prepared for SPF testing according to the method described below.

Example 3 The solution was applied to the epidermis of 8 side mice leg/c.
, 1 level. The epidermis was exposed to UV radiation in the tJ V-B and t, J V-A regions and compared to similarly exposed unprotected skin. The average test results for SPF are listed in Table 2.

344.28 117.8 1゜4
1.43. 35 note hawk 11 艷i00$ DMI
<1. , O<1.0 G O In addition to their use in skin surface coatings for sun protection, the compositions of the present invention may
Lacquers and soft resins for the manufacture of furniture and automatic abrasives,
The compounds of the present invention can also be used in various formulations such as cosmetics, lipsticks, hair treatments, skin formulas, silanes and contact lenses.The compounds of the invention act as brightening agents and provide broad-spectrum protection. may be used singly or in combination.

Fukishita's formulations are illustrative of just a few of the many applications.

Production Example 4゜Decaglycerol monolaurate polypropylene (200) monooleate ethoxylation (
10) Lanolin Alcohol Propylene Glycol Ethyl Alcohol (Anhydrous) Protein Polypeptide (2oz Alcohol Solution) Isopropyl Myristate 5.0 2.0 3.0 1.0 2.0 39.5 1.2 1.3 Propellant 11 15 .0 Propellant 12 30.0 Water
Wakachiyo articulation method: Dissolve all ingredients in slightly warmed ethyl alcohol, add water while preventing loss of alcohol, and stir thoroughly to disperse haze.

Filter the concentrate and fill into an aerosol container. Add propellant.

Production example 65 Carnauba wax 3 Candelilla wax 7 Ozogerito (Ozoker)
i Le ■) 3 Beeswax
7 lanolin
10 castor oil
60 Isopropyl Myristate 5 Fragrance
Some amount 7・wo 4.251 DC531shi! Add 1 piece of J Co-7Fi slowly to the mixture while stirring at high speed.

5. Cool to 40-45°C while continuing stirring.

6. Homogenize.

10.001 kerosene 16.50g Stoddard solution 5z manufacturing example 5 9 parts 50.00$ water Manufacturing method; 1. Dissolve the wax in Part A (85-90°C).

2. Add component B to the melted wax and stir twice to mix thoroughly. Return temperature to 85-90°C.

3. Add part C to the part A/part B mixture and mix with moderate stirring until homogeneous. Maintain temperature at 85-90°C.

4. Heat part D to 95°C and add Urethane 601 N, V, 32 long oil full #F 601 N, V, 352 TriLon X-457,5 Nu
xtra') Calcium 6z12 Bentone Diel 81
,, 28 Manufacturing example 116 in which bentone gel is dispersed under a high-speed concentrator and the following materials are added Low odor inorganic alcohol 85 Cyclodex ((yclodex) cobalt 6 $ 3 JK 27
0-70π 76 water
205 Anti-skin Z viscosity ・80-8
5 KU H/C・7.84 80' Gloss: 85 SAG・6ml Dain Takumi LO-Barafin Wax Part A 50% Paraffin Wax and Drosorbitan Monostearate) 5z Production Example 6 Part B 4oz Water Production Method 1 , Part A ingredients are melted together and heated to 80°C.

2. Heat part B to 85°C.

3. Add part B to A while stirring at 311°C until conversion occurs.
Add to parts. Rapidly add remaining water.

4. Cool to approximately 35°C with slow stirring in a cold water bath.

^mber Wax-Petrolite Cor
p,))30$su)<7■60/tween■60(7
8/22) 5z production example 2 B part 62z water! li! Manufacturing method: 1. Melt the A part components together and heat to 80-90°C.

2. Heat part B until boiling.

3. Slowly add Part B to Part A with moderate stirring until conversion occurs. After rapidly adding the remaining water, stop heating and allow to cool to room temperature without stirring.

41. , 0/H Luna Lava Wax Part A; 10π Carnauba Wax 5z Production Example 3 Part B 2 82$ Water Production Method: 1. Melt the Part A components together and heat to 95% and maintain.

2. Heat part B until boiling.

3. Slowly add Part B to Part A with moderately rapid stirring until conversion occurs. Rapidly convert remaining water.

4. Stop heating the emulsion and rapidly cool it while stirring. i
M 9fp Bridge 72 (IC + Americas, surfactant) 3.8
6 Giricon oil, 350cs (Rugel) 3
．． 00g# made PA7 5
．． 00 Ubisul ([Ivinul■) M-, 10 (OA
SF) 3.00B water 4
8.08 C Sodium hydroxide (10π aqueous solution) 0.4
Production method: (A) is heated to 60°C. (B) at 65℃
Heat to. Add (B) slowly to (A) with moderate stirring 9. Add (C). Cool to 50°C.

Add (D). Cool to 35° C. with stirring.

Stearyl alcohol 2.50 Silicone oil, 350 cs (Rugel) 5.00 Allurasolve 200 (IC Ri) 2.10 Bridge 72 (rcI) 4.90 Production Example 1
5.00 Production example 2
3.00B water 70.
00 Carbobol C Sodium hydroxide (10x aqueous solution > 0.2
0D Dovisil 200 (Dough) 0.
10 Manufacturing method: Heat (A) to 65°C. (B) 70
Heat to 'C. Add (B) to (A> with moderate stirring. Add (C). Cool to 50°C.

Add (D). Cool to 35° C. with stirring.

reject Add (D). Cool to 35° C. with stirring.

A Alramor E (ICri 7.
00 Stearyl Alcohol 2.50 Silicone Oil, 350cS (Rugel) 5.00 Bridge 72 (IC Ri) 4.90 Production Example 7 8.00B Water
70.00 Carbo Ball ■934 (B, F, Gutudrich) G,
ZOC sodium hydroxide (1oz aqueous solution) 0
．． 20D Dovisil 200 (Dough)
0, 1.0 Manufacturing method: Heat (A) to 60°C.

Heat (B) to 65°C. While stirring moderately (B)
Add slowly to (A). Add (C). 50
Cold bridge 721 (ICI) in °C
1.18 Bridge 72 (ICI)
3.86 manufactured 13i11B
s, o.

Silicone oil, 350es (Rugel) 3.0
0B Water 49.08 Carbo Ball 934 (B, F, Gutudrich) 040C
Sodium hydroxide (1oz aqueous solution) 0.40
D Dovisil 200 (Dough) o
,i.

Manufacturing method: Heat (A) to 60°C. (B) at 65°C
Heat to. 3. Slowly add (B) to (A) while stirring once. Add (C). Cool to 50"C. Add (D). Cool to 35"C with stirring.

Dog 111 Rune Screen Lotion Ai-e Flood King's Consideration Weight % A Alramor E (
ICr) 7.00 Stearyl alcohol 2.50 Silicone oil, 350cs (
Lugel) 5.00 Alura'/Lube ■200 (
lCr) 2.10 Bridge 72 (IC
I) 4.90 Production Example 5
5.50B water
72.50 Carbo Ball 93
4 (B, F, Gutdrich) 0.2QC Sodium hydroxide (10g aqueous solution) 0.20D Dovisil 200 (dough) 0.10 Production method: (A
) to 65°C. Heat (B) to 70°C. Add (B) slowly to (A) with moderate stirring.

Add (C). Cool to 50°C. Add (D). Cool to 35° C. with stirring.

Claims (1)

[Claims] 1. Formula (I) RCOCH_2CO-A-COCH_2COR^1(
I) [wherein -R and R' are both straight and branched alkyl groups having 1 to 10 carbon atoms or CR^2
R^3Ar (wherein R^2 and R^3 are H and 1~
selected from alkyl groups having 4 carbon atoms, Ar
is phenyl or is an alkyl-substituted phenyl group), and -A- is of formula II or of formula
III ▲There are mathematical formulas, chemical formulas, tables, etc.▼II▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼III (In the formula, R^4, R^5, R^6, R^7 are H or an alkyl group having 1 to 10 carbon atoms, or 1 to
(independently selected from alkoxy groups having 10 carbon atoms, but only one of the R^4, R^5, R^6, R^7 groups is an alkoxy group) 1,
selected from 3- or 1,4-benzene radicals]
A method for protecting a substrate from the effects of ultraviolet radiation, comprising topically applying a composition comprising a carrier admixed with an effective amount of an ultraviolet absorbing compound having a composition. 2, -A- is 1,4-phenylene, R, R^1 is tert-butyl, R^4, R^5, R^6 and R^
The method according to claim 1, wherein 7 is halogen. 3, -A- is 1,4-phenylene, R and R^
1 is iso-propyl, R^4, R^5, R^6
2. The method of claim 1, wherein and R^7 are halogen. 4, -A- is 1,3-phenylene, R and R^
2. The method of claim 1, wherein 1 is iso-propyl and R^4, R^5, R^6 and R^7 are halogen. 5, -A- is 1,3-phenylene, R and R^
2. The method of claim 1, wherein 1 is tert-butyl and R^4, R^5, R^6 and R^7 are halogen. 6, -A- is 1,4-phenylene, R and R^
2. The method of claim 1, wherein 1 is isoamyl and R^4, R^6, R^6 and R^7 are halogen. 7, -A- is 1,4-phenylene, R and R^
1 is ethyl, R^4, R^5, R^6 and R^
2. The method of claim 1, wherein 7 is halogen. 8, -A- is 1,4-phenylene, R and R^
2. The method of claim 1, wherein 1 is isobutyl and R^4, R^5, R^6 and R^7 are halogen. 9. The method of claim 1, wherein an auxiliary compound is mixed into the composition in an amount ranging from about 0.1 to about 50% by weight. 10. The method of claim 1, wherein said compound is mixed into said composition in an amount ranging from about 1 to 15%. 11. Claim 1, wherein said compound is soluble in said carrier.
Method described. 12. The method of claim 1, wherein the carrier is an aqueous emulsion. 13. The method of claim 1, wherein the substrate is the skin of a warm-blooded animal. 14, Formula (I) RCOCH_2CO-A-COCH_2COR^1(
I) [wherein R and R^1 are both straight and branched alkyl radicals having 1 to 10 carbon atoms or of the formula CR^
2R^3Ar (where R^2 and R^3 are H and 1
an alkyl group having ~4 carbon atoms, Ar is phenyl or an alkyl-substituted phenyl group), -A- is Formula II or Formula III ▲ Numerical formula, chemical formula, table, etc. ▼II ▲There are mathematical formulas, chemical formulas, tables, etc.▼III (In the formula, R^4, R^5, R^6, R^7 are H or alkyl having 1 to 10 carbon atoms, or 1 to 1
divalent 1, 3 or 1, independently selected from alkoxy groups having 0 carbon atoms, but with only one of those groups attached to the aromatic ring being an alkoxy group; A sunscreen composition comprising an acceptable carrier comprising a compound selected from 4 benzene radicals. 15. A composition comprising at least one compound selected from formula I and at least one other compound absorbing ultraviolet radiation in the range 290-400 mm.